1,3,5,7-tetramethyl-8-(10-methylanthracen-9-yl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: 1,3,5,7-tetramethyl-8-(10-methylanthracen-9-yl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
• 英文别名: 2,2-Difluoro-4,6,10,12-tetramethyl-8-(10-methylanthracen-9-yl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene；2,2-difluoro-4,6,10,12-tetramethyl-8-(10-methylanthracen-9-yl)-3-aza-1-azonia-2-boranuidatricyclo[7.3.0.03,7]dodeca-1(12),4,6,8,10-pentaene
• 化学式: C₂₈H₂₅BF₂N₂
• 分子量: 438.328
• InChiKey: BJXFDCSIEDGAMO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.15
• 重原子数：
  33
• 可旋转键数：
  1
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  7.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,3,5,7-tetramethyl-8-(10-methylanthracen-9-yl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene 在 氧气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 48.0h， 以5%的产率得到1,3,5,7-tetramethyl-8-((2aS,8bR)-8-methyl-1a,1b,2a,8b-tetrahydroanthra[1,2-b:3,4-b']bis(oxirene)-3-yl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  通过光诱导电子转移在 meso-anthra-BODIPY 中产生三重激发态：溶液和体外对单线态氧的荧光响应

  摘要：

  不含重原子的 BODIPY-蒽二元组 (BAD) 通过光诱导电子转移 (PeT) 产生局部激发的三重态，然后重组所得的电荷分离态 (CSS)。随后分子氧对三线态的猝灭产生单线态氧 (1O2)，其与蒽部分反应产生高荧光物质。BODIPY 亚基中烷基取代基的空间需求定义了 1O2 加成的位点。分离和表征了由蒽内过氧化物重排产生的新型双和四环氧化物和双环缩醛产品。在活细胞中通过 BAD 产生 1O2 可以实现二元组分布的可视化，有望成为新的成像应用。

  DOI：

  10.1021/jacs.7b00551
• 作为产物：
  描述：

  2,4-二甲基吡咯 、 10-甲基蒽-9-甲醛 在 三氟乙酸 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 三氟化硼乙醚 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以16%的产率得到1,3,5,7-tetramethyl-8-(10-methylanthracen-9-yl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene
  参考文献：
  名称：

  Design and Synthesis of a Library of BODIPY-Based Environmental Polarity Sensors Utilizing Photoinduced Electron-Transfer-Controlled Fluorescence ON/OFF Switching

  摘要：

  We systematically examined the mechanism of the solvent polarity dependence of the fluorescence ON/OFF threshold of the BODIPY (boron dipyrromethene) fluorophore and the role of photoinduced electron transfer (PeT). In a series of BODIPY derivatives with variously substituted benzene moieties at the 8-position, the oxidation potential of the benzene moiety became more positive and the reduction potential of the BODIPY fluorophore became more negative as the solvent polarity was decreased; consequently, the free energy change of PeT from the benzene moiety becomes larger in a more nonpolar environment. Utilizing this finding, we designed and synthesized a library of probes in which the threshold of fluorescence ON/OFF switching corresponds to different levels of solvent polarity. These environment-sensitive probes were used to examine bovine serum albumin (BSA) and living cells. The polarity at the surface of albumin was concluded to be similar to that of acetone, while the polarity of the internal membranes of HeLa cells was similar to that of dichloromethane.

  DOI：

  10.1021/ja068551y

文献信息

• Spin-Allowed Transitions Control the Formation of Triplet Excited States in Orthogonal Donor-Acceptor Dyads
  作者：Jason T. Buck、Andrew M. Boudreau、André DeCarmine、Reid W. Wilson、James Hampsey、Tomoyasu Mani

  DOI：10.1016/j.chempr.2018.10.001

  日期：2019.1

  Triplet excited states (triplets) serve as key intermediates in critical technologies and processes ranging from organic synthesis to biomedicine to molecular electronics. Production of triplets of π-conjugated organic molecules without heavy atoms remains challenging. Spin-orbit, charge-transfer intersystem crossing (SOCT-ISC) directly converts singlet charge-separated states to triplets in an electron

  三重态激发态（三重态）是从有机合成到生物医学再到分子电子学等关键技术和过程的关键中间体。没有重原子的三重π共轭有机分子的生产仍然具有挑战性。自旋轨道，电荷转移系统间交叉（SOCT-ISC）将单重态电荷分离态直接转换为电子供体-受体（DA）对中的三重态。在这里，使用一系列正交的DA型硼二吡咯亚甲基（BODIPY）衍生物作为模型系统，我们表明三联体的形成很大程度上受自旋允许的跃迁控制，而不是受SOCT-ISC的控制。然而，在（π，π*）状态之间，SOCT-ISC过程仍比普通ISC进行得快得多，这是因为SOCT-ISC的自旋轨道耦合强了2个数量级。我们进一步表明，这样的过程可以在非三重峰形成分子per中产生三重峰。我们的发现揭示了禁止自旋过程的明确物理基础，并为利用该过程的未来分子设计提供了指导。
• The Janus-faced chromophore: a donor–acceptor dyad with dual performance in photon up-conversion
  作者：Natalia Kiseleva、Mikhail A. Filatov、Michael Oldenburg、Dmitry Busko、Marius Jakoby、Ian A. Howard、Bryce S. Richards、Mathias O. Senge、Sergey M. Borisov、Andrey Turshatov

  DOI：10.1039/c7cc08930a

  日期：——

  An electron donor–acceptor dyad based on BODIPY (acceptor) and anthracene (donor) plays either the role of sensitizer or emitter in triplet–triplet annihilation photon up-conversion (TTA-UC). This Janus-like behavior was achieved via altering the relative ordering of charge-transfer and local excited state energies in the dyad through the polarity of TTA-UC media.

  基于BODIPY（受体）和蒽（供体）的电子供体-受体二元体在三重态-三重态an灭光子上转换（TTA-UC）中起敏化剂或发射剂的作用。通过改变TTA-UC介质的极性，改变二元组中电荷转移和局部激发态能量的相对顺序，可以实现这种类似于Janus的行为。
• Design and Synthesis of a Library of BODIPY-Based Environmental Polarity Sensors Utilizing Photoinduced Electron-Transfer-Controlled Fluorescence ON/OFF Switching
  作者：Hisato Sunahara、Yasuteru Urano、Hirotatsu Kojima、Tetsuo Nagano

  DOI：10.1021/ja068551y

  日期：2007.5.1

  We systematically examined the mechanism of the solvent polarity dependence of the fluorescence ON/OFF threshold of the BODIPY (boron dipyrromethene) fluorophore and the role of photoinduced electron transfer (PeT). In a series of BODIPY derivatives with variously substituted benzene moieties at the 8-position, the oxidation potential of the benzene moiety became more positive and the reduction potential of the BODIPY fluorophore became more negative as the solvent polarity was decreased; consequently, the free energy change of PeT from the benzene moiety becomes larger in a more nonpolar environment. Utilizing this finding, we designed and synthesized a library of probes in which the threshold of fluorescence ON/OFF switching corresponds to different levels of solvent polarity. These environment-sensitive probes were used to examine bovine serum albumin (BSA) and living cells. The polarity at the surface of albumin was concluded to be similar to that of acetone, while the polarity of the internal membranes of HeLa cells was similar to that of dichloromethane.
• Generation of Triplet Excited States via Photoinduced Electron Transfer in <i>meso</i>-anthra-BODIPY: Fluorogenic Response toward Singlet Oxygen in Solution and in Vitro
  作者：Mikhail A. Filatov、Safakath Karuthedath、Pavel M. Polestshuk、Huguette Savoie、Keith J. Flanagan、Cindy Sy、Elisabeth Sitte、Maxime Telitchko、Frédéric Laquai、Ross W. Boyle、Mathias O. Senge

  DOI：10.1021/jacs.7b00551

  日期：2017.5.10

  Heavy atom-free BODIPY-anthracene dyads (BADs) generate locally excited triplet states by way of photoinduced electron transfer (PeT), followed by recombination of the resulting charge-separated states (CSS). Subsequent quenching of the triplet states by molecular oxygen produces singlet oxygen (1O2), which reacts with the anthracene moiety yielding highly fluorescent species. The steric demand of

  不含重原子的 BODIPY-蒽二元组 (BAD) 通过光诱导电子转移 (PeT) 产生局部激发的三重态，然后重组所得的电荷分离态 (CSS)。随后分子氧对三线态的猝灭产生单线态氧 (1O2)，其与蒽部分反应产生高荧光物质。BODIPY 亚基中烷基取代基的空间需求定义了 1O2 加成的位点。分离和表征了由蒽内过氧化物重排产生的新型双和四环氧化物和双环缩醛产品。在活细胞中通过 BAD 产生 1O2 可以实现二元组分布的可视化，有望成为新的成像应用。